Patent GB-938118-A (GB)
Title: Organic liquids having increased electrical conductivity
IPC: C09B50/00
Filed: 1960-05-25
Abstract: The electrical conductivity of liquid hydrocarbons is increased by the addition of (a) a salt of a metal of atomic number 21-29 and an aromatic carboxylic acid or a sulphonic acid, the salt having a molecular weight of at least 200 and (b) an oil-soluble nitrogen containing copolymer, at least one of the monomers having an aliphatic chain of at least 8 carbon atoms, the copolymer having a molecular weight of 5,000 to 2,500,000 and a nitrogen content of 0,1-8% by weight, the weight ratio of copolymer (b) to the metal content of the salt (a) being 20-5,000:1.  The hydrocarbon may be a petroleum distillate boiling in the range -40 to 375 DEG C., e.g. gasoline, kerosine or jet fuel. The metal salt (a) may be of chromium, vanadium, iron, cobalt, or manganese, preferably in a trivalent state, and a petroleum or naphthalene sulphonic acid, a sulphonated dialkyl ester of an aliphatic dicarboxylic acid or an alkylated hydroxy aryl carboxylic acid, especially alkylated salicylic acids.  The latter are preferred having a C8+ alkyl substituent and the salt may be neutral or basic and contain minor amounts of the corresponding alkylated phenol.  The concentration of the salt may be 1 X 10-3 to 1 X 10-9 gram atom of metal per litre of hydrocarbon.  Calcium dioctylsulphosuccinate or similar synergist may also be added in an amount of 1 X 10-9 to 1 X 10-4 mol. per litre. Suitable copolymers are (1) of a nitrogen-free monomer having a C8-C18 aliphatic hydrocarbon side chain and a monomer containing a basic amino group, the copolymer containing 0,1-3,5% by weight basic amino nitrogen, e.g. lauryl methacrylate, styrene, diethylaminoethyl methacrylate in the ratio 45:45:10 (described in U.S.A. Specification 2,737,452); (2) of an N-vinyl-2-pyrrolidone (5-35%) and an acrylic ester of a C8+ alcohol, the ratio of N-vinyl-2-pyrrolidone to methacrylate preferably being 1:5 or 6 (described in Belgian Specification 550,442 and Canadian Specification 560,549); (3) a copolymer of a C10+ alphaolefin and an acrylic ester of a C1-3 alcohol in which at least 10% of the ester groupings have been amidized with a compound containing a -NR2 or -CONR2 (R=hydrocarbon) group (described in U.S.A. Specification 2,800,452); (4) of (a) an oil-solubilizing compound having an ethylenic linkage and a C4-C30 aliphatic carbon chain and (b) an amide of an alpha, beta-unsaturated C3-C6 carboxylic acid (if (a) contains less than 8 carbon atoms a third C8+, component is also incorporated), the mol. ratio of (a) to (b) being 1-15:1 (described in Specification 759,517); (5) of a vinyl pyridine and an ester of an acrylic acid and a C10X aliphatic alcohol; preferably a mixture of two different esters is used, the esters being derived from alcohols differing by at least 4 carbon atoms and present in a mol. ratio of one to the other of 1:10 to 10:1 and there also being present an ester of an acrylic acid and a C1-C6 alkanol; the mol. ratio of vinylpyridine to esters may be 1:15 to 2:1 and the lower ester may form 10-75% mol. of the total esters (described in U.S.A. Specification 2,839,512).  Many suitable vinylpyridines, acids and alcohols and specific combinations are given.  Optionally a metal deactivator may be added, preferably containing the structure:  <FORM:0938118/III/1> in which R is a C1-C4 alkylene group, e.g. N,N1-disalicylidene-1,2-propanediamine or bis 1-acetonyl-ethylidene) ethanediamine added in an amount of 1-1,000 gram mols per gram atom of metal in the conductivity additive.ALSO:The following oil-soluble copolymers having a molecular weight of 5,000-2,500,000 and a nitrogen content of 0,1-8% by weight in which at least one of the monomers contains an aliphatic chain of at least 8 carbon atoms are described:-  (1) A nitrogen-free monomer having a C8-C18 aliphatic hydrocarbon side chain and a monomer containing a basic amino group, the copolymer containing 0,1-3,5% by wt. basic amino nitrogen, e.g. lauryl methacrylate/styrene/diethylaminoethyl methacrylate in the ratio 45:45:10 (U.S.A. Specification 2,737,452).  (2) An N-vinyl-2-pyrrolidone (5-35%) and an acrylate or methacrylate of a C8+ alcohol (Belgian Specification 550,442 and Canadian Specification 560,549).  (3) A C10+ alpha olefin and an acrylic ester of a C1-C3 alcohol in which at least 10% of the ester groupings have been amidized with a compound containing a -NR2 or -CONR2 (R=hydrocarbon) group (U.S.A. Specification 2,800,452).  (4) A vinyl pyridine and an ester of an acrylic acid with a C10+ alcohol.  Preferably a mixture of two esters is used derived from alcohols differing by at least 4 carbon atoms and in a mol. ratio of one to the other of 1:10 to 10:1 and there is preferably also present an acrylic ester of a C1-C6 alkanol forming 10-75% mol. of the total esters.  The mol. ratio of vinyl pyridine to esters may be 1:15 to 2:1 (U.S.A. Specification 2,839,512).  Many specific combinations are specified and examples given of the preparation of copolymers of stearyl and lauryl methacrylate with methyl or butyl methacrylate and methyl or ethyl vinyl pyridine in various ratios.ALSO:The preparation of chromium alkyl salicylates containing at least one C8 + alkyl group is described.  Alkyl salicylic acid or an alkali metal salt thereof is first prepared by (a) alkylating salicylic acid with an olefin in the presence of 90-98% sulphuric acid, boron trifluoride or zinc chloride, (b) subjecting a nuclear acylated salicylic acid to a Clemmenson reduction with zinc and hydrochloric acid or, preferably (c) alkylating a phenol, forming the alkali metal phenate and carboxylating with carbon dioxide by the Kolbe method; alkyl salicylic acid is separated from unconverted phenate and by-products by acidifying and extracting with ammonia or neutralizing the acid only with alkali metal hydroxide.  From a water-alcohol solution of alkyl phenols and alkyl salicylic acid the former can be extracted with pentane. The chromium salt is obtained by treating the alkali metal salt in a hydrocarbon or alcohol with an alcoholic solution of an inorganic chromium salt.  For this purpose there may be used pure alkali metal alkyl salicylate or the carboxylated product containing alkyl phenol or the latter treated with alkali metal hydroxide to form the phenate or treated with double the amount necessary to form the phenate.  The resulting chromium salt is respectively pure or contains alkyl phenol, chromium alkyl phenate or chromium alkyl phenate and an excess of bound chromium hydroxide.